International Journal of Advanced Research and Publications

ISSN: 2456-9992

Making Of Ceramic Membranes For Wastewater

Treatment Of Hydrocarbon
Mansoor Kazemimoghadam
Malek Ashtar University of Technology, Tehran, Iran,
mzkazemi@gmail.com

Abstract: Various types of liquid hydrocarbons are used.One of the problems of these hydrocarbons is the formation of hydrocarbon waste.
Wastewater polluting the environment and should remove hydrocarbon contaminants before discharge into the environment or reduced.
Different methods of physical, chemical, biological and thermal treatment of this type of wastewater is not a good performance.According
to membrane technology for wastewater treatment, in this study, two layers ceramic membrane was made.The membrane consists of two
base layers and the active layer was made. On the basis of various parameters such as percent alumina to kaolin, the baking temperature and
pressure of hydraulic presses for making the base layer were examined. The effect of these parameters on exudate flux and porosity of the
membrane was determined Created. The active layer of alumina was synthesized at 550 C on the base. The results showed that the supports
of calcined in 1200 C include of 60% alumina and 200 bar pressure is good strength.At this condition, The porosity of the support is 41%
and water permeability flux is 746 Kg/m2.hr. The performance of the membrane to remove waste oil to 88 per cent. The built-in membrane
performance compared to polymeric membranes showed better performance.

Keywords: hydrocarbon, membrane, ceramic, waste, treatment

1. Introduction and reduction [4]. In thermal treatment, increasing

One of the problems with the production of hydrocarbon
products is the organic waste generated in the production
process. Today, many regulations have been put in place to
prevent environmental contamination due to the discharge of
this type of wastewater into the environment. The presence
of organic compounds in one of the water the main sources
of pollution are aquatic environments. Water soluble or
suspended hydrocarbon components include compounds that
are harmful to many animals and plants. Hydrocarbon
emulsions in water are one of the main sources of
contamination caused by the production of these
hydrocarbon in aqueous media. The components in this type
of wastewater are hazardous to a wide range of animals and
plants. In Figure 1, the size of oil droplets in the wastewater
of these industries is given. Also, the concentration of
hydrocarbons in refinery units is about 10-300 mg / lit [3-1].
Figure 1: Concentration of hydrocarbon droplet size in
petroleum effluents
At present, there are several methods for treating this
wastewater, which include physical, chemical, thermal and
biological treatment. Physical purification causes physical
changes in the properties of the substances in the wastewater,
while their chemical nature does not change.
Physical treatments include gravity separation, air flotation,
oiling, evaporation, filtration, absorption of activated
charcoal, steam or air degreasing, and solvent extraction.
Chemical refining creates a change in the chemical
properties of the waste material that makes it easy to separate
them. Substances that are produced or due to chemical
changes in the wastewater or that they do not cause any
pollution (such as water production and carbon dioxide). The
most important chemical treatments include chemical
sedimentation, electrolyte recovery, ion exchange, oxidation
temperature causes some substances to decompose into
wastewater. Organic compounds decompose into carbon
dioxide, water and halides, or halogen gases. Due to the fact
that decomposition conditions are usually close to the critical
point of water, all wastewater is exposed to phase change
conditions, and thus in this case the treated water obtains
liquidation of vapors or returns the conditions to the original
state. . For this reason, thermal methods are often used to
remove solid waste. Thermal treatment in the industry is
usually carried out by wet-oxidation, super-critical oxidation
and burning methods [5]. In biological treatment of
microorganisms, changes in the properties of the substances
are given and it decomposes some of the compounds in the
wastewater. Organic compounds in this case are a source of
nutrients for microorganisms. The final product is microbial
decomposition of cell masses, carbon dioxide, water, halides,
nitrogen and sulfur. Often the decomposition of the
compounds is not complete, and molecules with a low
molecular weight such as alcohol, ketones and organic acids
are formed. Biological processes in the industry include
active sludge process, aeration or stabilization basins, fixed
film reactors and anaerobic processes. Gravitational
separation is the most common method for treating oily
wastewater. If the outflow does not meet the constraints
required, secondary treatment steps are used to reduce
dissolved, emulsified, and dispersed oil. The emulsion is
broken down by chemical materials, followed by a
sedimentation system for the separation of excess oil [6]. If
the chemical breakdown method is used well, the method
will be effective, but it will be difficult to handle in many
cases. Among the drawbacks of this method are the
following:
• The process is strongly sensitive to the change in
the quality of wastewater effluent.
• The need for adaptation in each site is required to
determine the type and amount of chemical
required.
• A large amount of sludge is produced.
• Appliances have a large size.
• It requires precise control and skilled operators to
achieve optimal operations.

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 International Journal of Advanced Research and Publications
ISSN: 2456-9992

• Depending on the application, the operating cost release of these materials. The characteristics of kaolin used
may be high. are shown in Table 1.
• Due to the acidification of the wastewater, there
may be corrosion problems. Table 1: Kaolin powder analysis
• Mechanical problems occur due to the cramps of
chemical injection lines. Components (%)
• The amount of uncontained solids in the turbulent SiO2 51.9
TiO2 0.1
flow increases. Al2O3 34.1
Fe2O3 1.4
Thermal treatment (evaporation or burning) is a suitable and K2O 0.8
universal method for many oil emulsions. Its disadvantages Na2O 0.1
are high energy costs and a low amount of evaporated steam L.O.I 11.6
Total 100
oil, which requires the purification of the liquid component
[7]. Coagulants and filtration are suitable for reducing the
high amount of oil and grease within a certain range of The feed process involves the production of oil from a
droplet sizes. The problems of this process are the gradual production plant with the specifications indicated in Table 2.
absorption of materials in the coagulation medium and into An ultrafiltration system according to Fig. 2 is also used to
the walls of the device. This will damage the device and evaluate the membrane function.
reduce its performance. The high amount of sludge produced
is one of the other problems of this method. However, as Table 2: Specifications of industrial wastewater used
noted, routine procedures such as biological, chemical and
physical methods for treating and adapting oily waste with Specifications Unit Wastewater
existing standards (less than 100 mg / l) are either not cost- TSS mg/lit 210
effective or costly. In the case of selecting different COD5 mg/lit as O2 456
processes for the treatment of oil waste, it can be said that a BOD mg/lit as O2 69
suitable process has the least cost, is easy to work with, and Oil & grease mg/lit 237
provides the desired output quality. Membrane methods In Turidity NTU 173
addition to the simplicity of the process and the cost of initial
Ph - 8
investment, production of high purity products that do not
depend on the quality of the wastewater are produced. Also,
these units are small in size and produce a small amount of
sludge. So now, membrane technology has been introduced
as the best way to treat wastewater produced by oil units.
The membranes that are currently in use are polymeric.
Polymer membranes usually get stuck during use. They
therefore need to be replaced, which increases operating
costs. Ceramic membranes are resistant to temperature,
physical and chemical temperatures compared to polymer
membranes, and they are less clogged and have much longer
life, but it is harder to make these membranes than polymers. Figure 2: Laboratory system used in empirical studies
In this design, a two-layer composite ceramic membrane
with Nano-cavities was designed and constructed that has a To evaluate the membrane that is placed in the membrane
good function in the treatment of wastewaters generated in tuberculosis, the main cycle of the feed tank begins. The
hydrocarbon production units [8]. process feed, which is the same industrial effluent, is
pumped by a centrifuge pump from the feed tank to the
2. Materials and equipment bottom of the membrane module and enters the membrane
Ceramic membranes used in this research are made of two entrance channels. It should be noted that the filtration is
main parts: carried out in the mode of flow velocity and the leakage
1- Support or ceramic base (microfiber) current is collected and the flow passes into the feed tank.
2- Active layer (ultra filter) For analyzing and analyzing the leaked material after each
test, the leak material is collected in the sample container [9].
The materials used to build the ceramic base and the active
layer used in this research is: Kaolin, alpha-alumina powder, 3. Flow Trace Measurement Method
bohemian solution, nitric acid, PEG powder. Measurement of the flux of all membranes has been done in
Alpha-Alumina powder with a particle size of less than 4 the ultrafiltration system. Pressure and temperature are
microns has been used to make alumina-silicate ceramic important factors in measuring flux. The two factors have
bases with different percentages. Bohemite was used as the been kept constant throughout all experiments. Experiments
starting material for the production of alumina gamma to were carried out at 25 ° C and 3 bars, and each test was
synthesize the active layer of alumina. In this research, repeated for 10 minutes and repeated twice. The flux density
alumina with a percentage of kaolin has been used to make is calculated using the following equation [10]:
the microfilter membrane. The alumina used in this study is
from Merck. In order to create a controlled porosity, PEG is Flux = (Infiltrated water (kg))/ (Time (h) * membrane cross-
used to form porous base during calcification with the section (m2))

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 International Journal of Advanced Research and Publications
ISSN: 2456-9992

4- Making Nano filter Membrane
Many of the ongoing research around the world are being
developed to improve membrane processes by introducing
new materials and technology. The membrane materials are
of varying modularity in both types of polymers and
minerals (ceramics, carbon, metal and glass). Each of them
has its own advantages and constraints, including the low
cost and high ability in separation for polymer membranes
and high mechanical and thermal resistance and the
uniformity of the distribution of pore size in ceramic
membranes. The purpose of this study is to construct an
ultrafiltration membrane with cavities less than 100 nm. The
desired membrane consists of two parts of the base and the
active layer. The base is a microfilter membrane [11].
distilled water, the surface of the membranes was dried and
again weighed. The porosity of the micro filters was obtained
according to the following relationships [13]:
Porosity = (pore volume) / (Total volume)
Pore volume = (wet weight - Dry weight)/ (Volume of liquid
filling)
The porosity test results of the bases are shown in Figures 3
and 4 in the different conditions assessed.
100 bar

porosity%
Microfiltration membranes are the most common type of α=40%
membranes. The size of their pores is in the range of 0.05 to α=60%
10 (micrometers). Microfiltration membranes may be made
from a large number of different materials based on organic α=80%
materials (polymers) or minerals (ceramics, metal and glass).
Ceramic membranes, of course, are commonly used (α or Υ) T (C°)
- alumina, carbon and molybdenum. In this part of the
research, the purpose of producing a type of microfiltration
membranes with high percentages of alumina combined with Figure 3: Porosity variations in terms of temperature in
Kaolin soil was through the baking reaction, which has high various percentages of alumina at 100 bar
resistance, porosity and high permeability. In face-up
experiments, the effect of three factors (hydraulic press
pressure, alumina-kaolin percentage and cooking
temperature) has been investigated. The second layer of the
membrane contains an active alumina layer to perform the
process of separating with nanoscale cavities. Description of
manufacturing process and evaluation are as follows.

5- Build the support

In this work, the effect of alumina percentage on kaolin
(40%, 60% and 80%), sintering temperature (1000, 1100 and
1200 ° C) and the pressure of hydraulic press (100 and 200
bar) to make ceramic microfilter membrane through the
cooking reaction The effect of these parameters on the
membrane fermentation and porosity was determined. In the Figure 4: 3D chart Porosity variations in terms of
first step for the construction of bases, three powder mixtures temperature in various percentages of alumina at 100 bar
of samples with a composition of% 40%, % 60% and% 80
alumina, % 3 polyethylene glycol (to interconnect the
particles of kaolin and alumina and also increase porosity)
200 bar
and the rest of the made kaolin Became The final powders
were prepared by means of a press machine with two
porosity%

pressures of 100 and 200 bar and heated at a temperature of α=40%

10 ˚C / min inside the furnace at 1000, 1100, 1200 ° C. Thus,
the bases made by this method are compressed with three α=60%
combinations of 40%, 60% and 80% of alumina, and three α=80%
temperatures of 1000, 1100 and 1200 ° C, as well as with
two different pressures of 100 and 200 bar, and a total of 18
ceramic types of alumina silicate were made. The samples
T (C°)
were made as discs with a diameter of 2 cm and a thickness
of 3 mm [12].

5.1. Microfilter porosity measurement Figure 5: Porosity variations in terms of temperature in

The porosity of the membranes made by saturation method various percentages of alumina at 200 bar
was measured by water test. First, the membranes were
heated to a temperature of 150 ° C to remove water from the
surface and the cavities inside it. Then, by measuring the
thickness and diameter of the micro filters, their dry volume
was obtained. The micro filters were then weighed and
distilled into a distilled water for a day or so until their
cavities were completely filled with water. After leaving the

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 International Journal of Advanced Research and Publications
ISSN: 2456-9992
Figure 6: 3D chart Porosity variations in terms of
temperature in various percentages of alumina at 200 bars
According to the data obtained, it is clear that at constant
sintering temperature, increasing the percentage of alumina
used in the initial powder increases porosity. This increase is
due to the fact that higher alumina percentages require higher
temperatures for complete sintering. As a result, the sintering
is not complete and the membrane-forming particles are less
consistent. Also, the size of the used alumina particles can be
noted, which is larger than the size of the kaolin particles in
the powder, which results in a higher percentage of these
particles, lower density and porosity. Another reason that can
be mentioned for increasing porosity with increasing alumina
is the formation of the molybdenum phase, is a silicate-rich
middle liquid, which, by using this liquid phase, prevents the
formation of the glass phase after cooling, and prevents
porosity reduction. The cause of porosity reduction by
creating a glass phase is that if formed, the liquid phase will
flow through the cavities and block them. According to
Figures 3 and 4, in percentage of alumina, with increasing
sintering temperature, porosity decreased, indicating that the
materials are more sintered at higher temperatures, which
results in more material condensation and hence reduced
porosity. As expected, with increasing hydraulic press
pressure, the porosity decreases significantly, indicating that
the primary powder is compressed by applying more
pressure, which reduces porosity after sintering.
5.2. Flow Test Results and Analysis:
Since the formation of the mullite phase at temperatures
above 1200 ° C, the micro filters formed at temperatures
below this temperature did not have the required physical
strength to place in the modulus and do not test the flux on
them, and therefore, the flux meters were tested only at a
temperature 1200 ° C with 3% of different alumina
compositions and two different pressure presses of 100 and
200 bar.
Table 3: Flow Test Results
Pressure
100 bar 200 bar
press
Alumina 40 % 60 % 80 % 40 % 60 % 80 %
Flux
1388.2 1289.2 941.7 1332.9 746.7 748.9
(Kg/m2.hr)
According to the results obtained at constant steady-state
sinking temperature (1200˚C), with increasing alumina
percentage, flux decreased; this may be due to the formation
of more openings of cavities, when used with higher alumina
in micro filters, these cavities one stop prevents the flake of
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water. As expected, with the increase in hydraulic press
pressure, the fluctuation flux has also declined markedly.
The results of this study show that the calcined micro filters
at 1200 ° C with alpha-alumina of 60% and the hydraulic
pressure press bar 200 have an appropriate strength. In this
case, the membrane porosity is 41% and the flux of distilled
water equals to 8.8 Kg / m2.hr. 746 and was determined as
the optimum base for the synthesis of the active layer of
alumina.
5.3. Hydraulic Pressure Effect
Increasing the pressure of the press causes more adhesion to
the material, which is itself a factor in closing empty spaces
and also prevents the formation of more cavities. Due to the
direct relationship between the parallelogram and trap flux,
decreasing the porosity in the membrane also reduces its
flux. The effect of these two factors on the reflectivity and
porosity is shown in Figures 3 and 4, as well as Table 3.
5.4. Effect of Kaolin
As expected, porosity and shading increases with the
addition of kaolin to the mixture. This is due to the fact that
the size of the alumina particles is larger than that of the
kaolin particles. Alumina also reacts to the liquid phase and
prevents the formation of a mild liquid phase, which prevents
the foam from blocking after cooling the liquid.
5.5. Structural X-ray diffraction (XRD) X and scanning
electron microscopy (SEM)
X-ray diffraction (XRD) is an effective way of identifying
the unknown phases of a powder mixture containing several
crystal types. The analysis is done by comparing the
diffraction of an unknown sample with a given sample. XRD
is an important method for evaluating ceramic materials that
provides the analysis of materials during the manufacturing
process. In this research, each sample was analyzed
individually by the Philips-PW3710 with a Cuka wavelength
of 1.54 with an X-ray machine. The membrane surface was
also studied by scanning electron microscopy (SEM) to
better determine the structure of the membrane. Figure 5
shows scanning electron microscopy images of an optimal
sample, including the sample cross-section and the sample
surface. In Figure 6, the x-ray diffraction pattern is
presented. Different phases of the alumina-silicate formed in
the sample are shown.
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 International Journal of Advanced Research and Publications
ISSN: 2456-9992

7. Wastewater treatment test:

He wastewater treatment test was performed using the
described laboratory system. To determine the performance
of the membrane and the separation rate, the process feed
and sample passed through the COD test membrane.

7.1. Results of the wastewater treatment test and its

analysis:
The results of the COD analysis of leakage and flow of the
synthesized membrane are presented in Table 4.

Table 4: COD Test Results

Removal
Feed - COD Permeate- COD
percentage in the
(mg/lit) (mg/lit)
membrane
550 65 88.18

According to the obtained result, the synthesized layer at 550

° C showed a good performance in the separation of the
tested hydrocarbon emulsion. To evaluate and compare the
performance of commercial polymer membranes, a PVDF
Figure 5: Micrographs of SEM made from mallite-alumina plate polymer membrane was used. The membrane
ceramic membrane (60% alumina and 40% kaolin) a. Level characteristics used in Table 5 are.
b Cross-section
Table 5: Specifications of the polymer membrane used
Counts
Corundum, syn; Al2 O3

Corundum, syn; Al2 O3

M1.CAF

Properties PVDF
Corundum, syn; Al2 O3

1500
Quartz, syn; Si O2; Corundum, syn; Al2 O3

MW 20000
Quartz, syn; Si O2; Corundum, syn; Al2 O3
Corundum, syn; Al2 O3

1000
Corundum, syn; Al2 O3

Pore Size 30 nm
Quartz, syn; Si O2; Corundum, syn; Al2 O3
Corundum, syn; Al2 O3

Commercial polymer membrane test was used for

Corundum, syn; Al2 O3

500

purification of wastewater under conditions similar to

ceramic specimens. Table 6 shows the percentage of COD
0
10 20 30 40 50 60 70
removal from the wastewater sample and the percentage of
Position [°2Theta] removal in the membrane of ceramic membranes made with
commercial samples.
Figure 6: XRD from a membrane sample containing 20%
kaolin and 80% alumina
Table 6: Comparison of the membrane separation function
6. Making Nano-filter active layer made with existing commercial polymer specimens
The boehmite solution is alkoxide. This solution is due to the
fact that it is a mixture of bohmite and pseudo-boehmite Perce
Remov
particles, the particles of which are interconnected, and so is ntage
al
the instability of the solution; therefore, to prepare for the polyme remo Cerami
percent
r val in c
membrane, this crude solution should be put into peptic Parame
Unit Feed membr the membr
age in
operation. By pepticisation, the particles are separated and ter cerami
ane poly ane
c
dispersed as fine particles in solution, and the bohemian output mer output
membr
solution will be unstable to a stable state. For pepticisation, mem
ane
brane
the mixture was first mixed with a molar HNO3 / AlOOH mg/li
molar ratio of 0.07 Nitric acid and then uniformly stirred for COD 550 190 65.45 65 88.18
t
1 hour at a temperature of 90 ° C for 12 hours under reflux in
the autoclave. With the probability that the alcohol remained As can be seen from the table results, the performance of the
inside the solution, the solution was taken at about 90 ° C for polymer membrane for the removal of pollutants from the
about 2 hours. The solution obtained is called tuberculosis wastewater sample is about 65%, while the sample made
[16-14]. The aluminacylate bases prepared from the previous about 88% of the elimination of pollutants and the quality of
step are placed in a Bohemite solution for 1 minute and then the effluent is COD Less than 100 milligrams per liter is
the samples are dried at ambient temperature for 24 hours. consistent with environmental standards.
The coated bases were then calcined for 5 hours at 550 ° C
for 3 hours.

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 International Journal of Advanced Research and Publications
ISSN: 2456-9992

8. Conclusion products Processing. 2013, 91, 473–480.

The results showed that the ceramic membrane made a good
function to reduce the COD of hydrocarbon effluents created
during the production of hydrocarbon. This ceramic
membrane showed better performance compared to
commercial polymer membranes. The removal rate of
pollutants in the ceramic membrane was 88%, which was
much better than 65% of commercial polymer membranes.
Also, using this type of membrane, the COD can produce
hydrocarbon effluents less than 100 milligrams per liter and
comply with environmental standards.
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